AI Article Synopsis
- Researchers developed the first chiral helicene-NHC gold(I) complexes that excel in enantioselective catalysis, utilizing a unique L-shaped chiral ligand.
- The synthesis involved a key post-functionalization step, introducing chiral elements into a racemic mixture of complexes with central, axial, and helical chirality.
- After conducting HPLC for enantiomeric resolution, the complexes were structurally characterized using X-ray crystallography and theoretical calculations, showcasing their efficacy in asymmetric catalysis with impressive results in cycloisomerization.
Article Abstract
The first chiral helicene-NHC gold(I) complexes efficient in enantioselective catalysis were prepared. The L-shaped chiral ligand is composed of an imidazo[1,5-a]pyridin-3-ylidene (IPy) scaffold laterally substituted by a configurationally stable [5]-helicenoid unit. The chiral information was introduced in a key post-functionalization step of a NHC-gold(I) complex bearing a symmetrical anionic fluoreno[5]helicene substituent, leading to a racemic mixture of complexes featuring three correlated elements of chirality, namely central, axial and helical chirality. After HPLC enantiomeric resolution, X-ray crystallography and theoretical calculations enabled structural and stereochemical characterization of these configurationally stable NHC-gold(I) complexes. The high potential in asymmetric catalysis is demonstrated in the benchmark cycloisomerization of N-tethered 1,6-enynes with up to 95 : 5 er.
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| http://dx.doi.org/10.1002/chem.202200166 | DOI Listing |
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